Self-healing and scratch resistant shape memory polymer system

ABSTRACT

An exemplary embodiment discloses a polymer system including a shape memory polymer material and a graphene material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.12/273,083 filed Nov. 18, 2008.

TECHNICAL FIELD

The field to which the disclosure generally relates includes polymericmaterials, and more specifically to a shape memory polymeric materialsystems that can fix to one or more deformed temporary shapes andrecover to their original shape only upon external stimuli.

BACKGROUND

Shape memory polymers (SMPs) represent responsive polymers that can fixto deformed temporary shapes and recover to their permanent (original)shapes only upon external stimuli.

SUMMARY OF EXEMPLARY EMBODIMENTS OF THE INVENTION

One exemplary embodiment may include a polymer material system thatincludes a shape memory polymer and a graphene material.

An exemplary method for improving the scratch resistance and selfhealing capabilities of a polymeric system including a shape memorypolymer material includes adding a graphene material to the shape memorypolymer material.

An exemplary method may include forming a polymer system including ashape memory polymer material having a graphene material, transformingthe polymer system from its permanent shape to a temporary shape, andcoupling the polymer system in the temporary shape to at least onesubstrate material. The at least one substrate material may besubsequently uncoupled by transforming the polymer system back to itspermanent shape.

Other exemplary embodiments of the invention will become apparent fromthe detailed description provided hereinafter. It should be understoodthat the detailed description and specific examples, while disclosingexemplary embodiments of the invention, are intended for purposes ofillustration only and are not intended to limit the scope of theinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

Exemplary embodiments of the invention will become more fully understoodfrom the detailed description and the accompanying drawings; wherein:

FIG. 1A is a perspective view of a polymeric material according to oneexemplary embodiment having shape memory effect and in its originalpermanent shape;

FIG. 1B is a perspective view of the polymeric material of

FIG. 1A transformed to a temporary shape;

FIG. 1C is a perspective view of the polyrneric material of FIG. 1Atransformed to a temporary shape and coupled between a pair ofsubstrates;

FIG. 2 is a graphical illustration of a load versus displacement plotfor shape memory polymer systems having increasing amounts of graphene;

FIG. 3 is a table comparing the elastic modulus of the shape memorypolymer systems as determined from the graphical illustration of FIG. 2;

FIG. 4 is a table comparing the hardness of the shape memory polymersystems as determined from the graphical illustration of FIG. 2;

FIG. 5A illustrates a shape memory polymeric material according to oneexemplary embodiment prior to indention;

FIG. 5B illustrates the shape memory polymeric material being indentedby a Vickers Indentor;

FIG. 5C illustrates the shape memory polymeric material of FIG. 5A afterindention by the Vickers Indentor; and

FIG. 6 is a graphical illustration of a coefficient of friction analysisat various points of a 2 millimeter scratch introduced to the of theshape memory polymer systems formed by a scratch test.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The following description of the embodiment(s) is merely exemplary(illustrative) in nature and is in no way intended to limit theinvention, its application, or uses.

Referring first to FIGS. 1A-1C, a polymeric material 20 having shapememory effect (SME) may be illustrated in its original permanent shape(shown as 20A in FIG. 1A) and in a first temporary shape (shown as 20Bin FIGS. 1B and 1C).

The polymeric material 20 may formed from a shape memory polymer 22 anda graphene material 24, wherein the graphene material is in the range ofabout 0.005 to 2 weight percent of the polymeric material.

By definition, the permanent original shape 20A is the shape in whichthe polymeric material 20 will remain in the absence of deformationunder load and elevated temperatures as will be described in furtherdetail below.

To obtain the first temporary shape 20B from the original shape 20A, thepermanent shape 20A may be heated to a first elevated temperatureT_(high) and then deformed under stress to yield the first temporaryshape 20B, a shape which may be different in visual appearance from thepermanent shape 20A. By definition, the first elevated temperatureT_(high) is a temperature sufficiently high to ensure a phase transitionfor the shape memory polymer material 22 (i.e. is a temperature abovethe glass transition temperature (T_(g)) of the shape memory polymermaterial 22). The polymeric material 20 may then be cooled under stressbelow T_(high), wherein the stress may be relieved to fix the firsttemporary shape 20B. To recover the permanent shape 20A from the firsttemporary shape 20B, the polymeric material 20 may be reheated to thefirst elevated temperature T_(high) in the absence of stress.

Graphene, as defined herein, is a one-atom-thick planar sheet ofsp2-bonded carbon atoms that are, densely packed in a honeycomb crystallattice. A graphene material 24 may include one or more layers, but lessthan 10 layers, of graphene stacked onto each other.

Free standing graphene may be prepared in a microwave plasma enhancedchemical vapor deposition technique. Graphene may also be produced byother chemical vapor techniques such as thermal chemical vapordeposition (CVD), radio frequency plasma CVD, or direct current CVD. Inthese chemical vapor techniques, carbon containing precursors, such asacetylene or methane or ethylene, may be mixed with hydrogen at adeposition pressure of between about 40 and 100 torr and a growthtemperature of between about 400 and 1000 degrees Celsius. The grapheneparticles may be collected by silicon and a graphite plate, or any othersubstrate that will not react with carbon in the growth temperaturerange.

The shape memory polymer material 22 may be formed, in one exemplaryembodiment, from a rigid aromatic diepoxide (EPON 826), a flexiblealiphatic diepoxide such as neopentyl glycol diglycidyl ether (NGDE),and an aliphatic diamine curing agent such as poly(propylene glycol) bis(2-aminopropyl)ether (Jeffamine D-230).

To form the polymeric material 20, in accordance with one exemplaryembodiment, the graphene materials 24 are admixed with Jeffamine D-230in an ultrasonic bath for about 30 minutes. EPON 826 was melted at about75 degrees Celsius for 15 minutes. The melted EPON 826 was then mixedwith the NGDE and Jeffamine D-230 (with the graphene material 24) at amole ratio of about 1.6/0.4/1.0 to form a mixture. The mixture was thenpoured into a mold (not shown), cured at about 100 degrees Celsius forabout 1 hour, and post-cured at about 130 degrees Celsius for about 1hour to produce a shape molding polymer/graphene nanocomposite (i.e. thepolymeric material 20). The cured polymeric material 20 was demolded andcut to a desired shape and size.

The introduction of a small amount of graphene material 24 to the shapememory polymer 22 provides several potential advantages to the shapememory polymer.

For example, the introduction of small amounts of graphene material 24to the shape memory polymer 22 prepared as described may improve thetoughness, and/or the hardness, of the polymeric material 20.

To test the toughness and hardness, samples of polymeric materials 20having the same composition of shape memory polymeric material 22 andhaving varying levels of graphene material 24 were prepared andseparately tested for toughness (elastic modulus) and hardness using aVickers Indentor, available from CSM Instruments, Inc. of Needham,Mass., may be utilized.

To test for toughness and for hardness, as shown in FIGS. 5A-5C, anindenter tip 71 of a Vickers Indentor 73 may be situated normal to thepolymeric material sample surface 23, as shown in FIG. 5A. The indentertip 71 may then be driven into the sample 20 by applying an increasingload up to a predefined value, as shown by arrows 75 in FIG. 5B. Theload may then be decreased until the tip 73 is, free of the material.20, therein forming the scratch 77 in the polymeric material 20 as shownin FIG. 5C.

The resultant load-depth curve created by the process shown in FIGS.5A-5C, as shown in FIG. 2, may then be used to calculate mechanicalproperties such as elastic modulus, as shown in table form in FIG. 3,and hardness, as shown in table form in FIG. 4.

As shown in FIG. 3, the Modulus of the shape memory polymer material 22(i.e. without graphene) measured at about 4.2 GPa, while theintroduction of about 0.005 weight percent of graphene material 24increased the Modulus to about 4.9 GPa. Moreover, the introduction ofabout 0.025 weight percent of graphene material 24 increased the Modulusto about 6.7 GPa.

As shown in FIG. 4, the hardness of the shape memory polymer material 22(i.e. without graphene) measured at about 22 Vickers, while theintroduction of about 0.005 weight percent of graphene material 24increased the hardness to about 26 Vickers, which suggests about an18.5% increase in hardness. Moreover, the introduction of about 0.025weight percent of graphene material 24 increased the hardness to about46 Vickers.

In addition, the introduction of small amounts of graphene material 24to the shape memory polymer 22 prepared as described above may alsodecrease the coefficient of friction at a designated scratch length inthe polymeric material 20, utilizing the Vickers Indentor. The tipmaterial (commonly diamond or hard metal (WC)) of the Vickers Indentormay be drawn across the surface of the polymeric material 20 under aconstant load to scratch the surface of the polymeric material 20 to adesired depth for a given distance. The coefficient of friction may thenbe measured at various points along the length of the scratch.

The coefficient of friction measures the force of friction between thetip material of the Mentor and the polymeric material along the scratchlength that is introduced to the polymeric material after it is formedto a desired size and shape. Polymeric materials having a highercoefficient of friction may have a greater tendency to crack as a resultof the introduction of a scratch to its surface.

It is theorized that the lower surface friction may be the result of oneof two distinct or related phenomenons. First, the multi-layer structureof the graphene material 24 may serve as a solid lubricant to reducefriction along the scratch 77. The resulting low friction force mayreduce or avoid cracking generated along the scratch 77 as it isintroduced to the surface 23 of the polymeric material. 20.

Also, the graphene material 24 may increase fracture toughness due tothe strong interface interaction between the graphene material 24 andthe polymer matrix 22. This interface interaction may improve scratchresistance, which may result in no crack observed along the scratch.

In addition, the enhanced mechanical properties by adding the graphenematerial 24 may improve the capability for shape recovery of thepolymeric material 20. Thus, if the indented polymeric material 20 ofFIG. 5C is reheated to an elevated temperature, the scratch 77 may belessened or eliminated, as shown transitioning from FIG. 5C back to FIG.5A.

Alternatively, the reduced coefficient of friction may be the result ofthe ability of the polymeric material to resist as scratch as it isapplied to the surface of the polymeric material Such resistance mayalso include the ability of the polymeric material to resist cracking inareas near the applied scratch.

Further, a combination of both theories may be present, wherein areduced coefficient of friction may be the result of the ability of thepolymeric material to resist the scratch as it is applied to its surfacefollowed by the ability of the polymeric material to “self-heal” asdescribed above.

FIG. 6 graphically compares the coefficient of friction at given scratchlengths for polymeric materials 20 formed and described above with andwithout small amounts of graphene material 24. In FIG. 6, the tipmaterial of the Vickers Indentor (similar to that shown in FIGS. 5A-5C)was drawn across the surface of the polymeric material 20 having varyinglevels of graphene material 24 (0, 0.005 weight percent, and 0.25 weightpercent) under a constant load of 5N to scratch the surface of thepolymeric material 20 to a desired depth in a distance of about 2millimeters.

As FIG. 6 illustrates, the introduction of increasing levels (from 0.005to 0.025) weight percent of graphene material 24 to the shape memorypolymer 22 to form the polymeric material 20 resulted in lowercoefficients of friction at virtually all scratch lengths between 0 and2 millimeters, therein suggesting that the introduction of small amountsof graphene material 24 may provide improved scratch resistance, orself-healing, of polymeric materials 20 having shape memorycharacteristics.

In one exemplary use, the polymeric material 20 of the exemplaryembodiments may be utilized to reversibly couple together one or moresubstrate materials. This may be accomplished by transforming thepolymeric material 20 from its permanent shape 20A, as shown in FIG. 1A,to its temporary shape 20B, as shown in FIG. 1B, and coupling thepolymeric material 20B to one or more substrate materials (shown as twosubstrate materials 26 and 28 in FIG. 1C). Subsequently, the one or moresubstrate materials may be uncoupled by transforming the polymericmaterial 20 from its temporary shape 20B back to its permanent shape 20Aas described above (and illustrated transitioning from FIG. 1C to FIG.1A). Thus, the polymeric material 20 of the exemplary embodiments mayfind an exemplary use in separating substrate materials 26 and 28 whilethey are being stored or transported. By increasing the toughness, orhardness, or scratch resistance of these polymeric materials 20 throughthe introduction of the graphene material 24, additional uses requiringthese improved performance characteristics may be realized. For example,the improved toughness may allow the polymeric material 20 to be coupledto fragile substrate materials that may chip or break if contacted toother fragile substrate materials during shipping or storage.

The above description of embodiments of the invention is merelyexemplary in nature and, thus, variations thereof are not to be regardedas a departure from the spirit and scope of the invention.

1. A product comprising: a shape memory polymer material; and a graphenematerial incorporated into said shape memory polymer material to form apolymer system; wherein said polymer system is capable of transformingbetween an original permanent shape and a temporary shape.
 2. Theproduct of claim 1, wherein said graphene material comprises a singlelayer of graphene.
 3. The product of claim 1, wherein said graphenematerial comprises between 2 and 10 layers of graphene.
 4. The productof claim 1, wherein said shape memory polymer material comprises anepoxy thermosetting polymeric material.
 5. The product of claim 4,wherein said epoxy thermosetting polymeric material comprises thereaction product of an aromatic diepoxide, an aliphatic diepoxide and analiphatic diamine curing agent.
 6. The product of claim 5, wherein themole ratio of said aromatic diepoxide, said aliphatic diepoxide, andsaid aliphatic diamine curing agent within said epoxy thermosettingpolymeric material is about 1.6/0:4/1.0.
 7. The product of claim 1,wherein said graphene material comprises between about 0.005 and 2weight percent of said shape memory polymer material.
 8. The product ofclaim 1, wherein said graphene material comprises between about 0.005and 0.025 weight percent of said shape memory polymer material.
 9. Amethod for improving the scratch resistance and self healing powers ofpolymeric material including a shape memory polymer material, the methodcomprising: introducing a graphene material to the shape memory polymermaterial.
 10. The method of claim 9, wherein said graphene materialcomprises between about 0.005 and 2 weight percent of the shape memorypolymer material.
 11. (canceled)
 12. The method of claim 1 wherein theshape memory polymer material comprises an epoxy thermosetting polymericmaterial, wherein said graphene material comprises between about 0.005and 0.025 weight percent of the shape memory polymer material.
 13. Themethod of claim 1 wherein said graphene material comprises between 1 and10 layers of graphene, wherein said graphene material comprises betweenabout 0.005 and 0.025 weight percent of the shape memory polymermaterial.
 14. A method comprising: forming a shape memory polymermaterial; introducing a graphene material to said shape memory polymerto form a polymer system, wherein said polymer system is capable oftransforming between an original permanent shape and a temporary shapeproviding at least one substrate material; providing said polymer systemin said temporary shape; coupling said polymer system in said temporaryshape to at least one of said at least one substrate materials.
 15. Themethod of claim 14, wherein said graphene material comprises betweenabout 0.005 and 2 weight percent of the shape memory polymer material.16. The method of claim 15, wherein said graphene material comprisesbetween 1 and 10 layers of graphene.
 17. The method of claim 13, whereinforming a shape memory polymer and introducing a graphene material tosaid shape memory polymer to form a polymer system comprises: providingan ultrasonic bath; mixing an aliphatic diamine curing agent and a smallamount of a graphene material in said ultrasonic bath; introducing anaromatic diepoxide and an aliphatic diepoxide to said aliphatic diaminecuring agent and said small about of said graphene material to form amixture; introducing said mixture to a mold; curing said mixture withinsaid mold; optionally post-curing said cured mixture within said mold;and removing said cured mixture from said mold.
 18. The method of claim17, wherein the mole ratio of said aromatic diepoxide, said aliphaticdiepoxide, and said aliphatic diamine curing agent within said mixtureis about 1.6/0.4/1.0.
 19. The method of claim 13 further comprising:transforming said polymer system from said temporary shape to saidpermanent shape; and uncoupling said polymer system in said permanentshape from said at least one of said at least one substrate materials.20. The method of claim 13, wherein said at least one substrate materialcomprises at least two substrate materials, wherein each of said at twosubstrate materials is each individually coupled to said polymer systemin said temporary shape.